Thermal ink jet ink composition

ABSTRACT

A thermal ink jet ink composition include a volatile organic solvent, a binder resin, a dye, a humectant in an amount from 1% to 40% by weight of the ink composition, and an additive for extending the decap time. The additive is present in an amount greater than 0.01% by weight of the thermal ink jet ink composition. The additive is selected from fluorinated surfactants, ionic surfactants, and nonionic surfactants.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Continuation-In-Part of U.S. application Ser. No.13/496,531 filed Mar. 16, 2012, now U.S. Pat. No. 8,920,552, whichclaims priority under 35 U.S.C. §371 from PCT Application No.PCT/US2010/050655, filed in English on Sep. 29, 2010, which claims thebenefit of U.S. Provisional Application No. 61/247,316, filed Sep. 30,2009, the disclosures of all of which are incorporated herein byreference in their entireties.

BACKGROUND OF THE INVENTION

Thermal ink jet (TIJ) print heads produce ink droplets from thermalvaporization of the ink solvent. In the jetting process, a resistor isheated rapidly to produce a vapor bubble which subsequently ejects adroplet from the orifice. This process is extremely efficient andreproducible. Modern TIJ print heads for industrial graphicsapplications are capable of generating uniform drops of 4 pL or smallerin volume at frequencies of 36 kHz or greater. Typical commercial TIJdevices are specifically designed to vaporize water or solvents thathave physical properties close to those of water (e.g. high boilingpoint, large heat capacity, low molecular weight).

Although TIJ printing systems have been available for over 30 years,most of the commercial inks available for thermal ink jet systems havebeen water-based, i.e. they contain more than 50% water. Such aqueousinks have one or more drawbacks such as long ink dry times or pooradhesion to semi-porous or non-porous substrates. Since around 2009 anincreasing number of solvent-based TIJ inks have been proposed orintroduced, with varying degrees of success. These formulas haveperformance and shelf-life limitations due to material incompatibilitywith traditional thermal ink jet cartridges.

There is a desire for inks with attractive performance characteristicssuch as short dry times, long decap times and good adhesion when using aTIJ system to print onto semi-porous and non-porous substrates.

BRIEF SUMMARY OF THE INVENTION

The invention provides a thermal ink jet ink composition including avolatile organic solvent, a binder resin, a dye, a humectant, and anadditive for extending the decap time. The thermal ink jet inkcomposition may provide increased decap time and short dry times.

In an embodiment, a thermal ink jet ink composition includes one or morevolatile organic solvents, one or more binder resins, one or more dyes,a humectant in an amount less than 40% by weight of the thermal ink jetink composition, and an additive for extending thedecap time. Theadditive is present in an amount greater than 0.1% by weight of thethermal ink jet ink composition. The additive is selected fromplasticizers, surfactants, aliphatic hydrocarbons, drying oils andmixtures thereof. The additive does not phase separate from the ink jetcomposition during application of the ink to a substrate in thermal inkjet printing.

In another embodiment, a method for printing images on a substrate witha thermal ink jet printer includes directing a stream of droplets of athermal ink jet ink composition to a substrate. The ink compositionincludes one or more volatile organic solvents, one or more binderresins, one or more dyes, a humectant in an amount less than 40% byweight of the thermal ink jet ink composition, and an additive in anamount greater than 0.1% by weight of the thermal ink jet inkcomposition. The additive is selected from plasticizers, surfactants,aliphatic hydrocarbons, drying oils, and mixtures thereof. The inkdroplets are allowed to dry, thereby printing an image on the substrate.The decap time of the ink is greater than 2 minutes.

In another embodiment, a thermal ink jet ink composition includes one ormore volatile organic solvents, one or more binder resins, one or moredyes, a humectant in an amount less than 40% by weight of the thermalink jet ink composition, and an additive for extending the decap time.The additive is present in an amount greater than 0.01% by weight of thethermal ink jet ink composition. The additive is selected from nonionicsurfactants and ionic surfactants.

In another embodiment, a thermal ink jet ink composition includes avolatile organic solvent; a binder resin, wherein the binder resin ispresent in an amount from 0.3% to 8% by weight of the ink composition; adye; a humectant in an amount from 1% to 40% by weight of the inkcomposition; and an additive for extending the decap time of the inkcomposition. The additive is present in an amount less than 0.1% byweight of the ink composition. The additive is selected fromperfluoropolyethers, modified perfluoropolyethers, glycol-basedperfluoroalkyl ethers, perfluoroalkyl substituted polyethers, andmixtures thereof. If water is present, it is present in amount less than10% by weight of the ink composition. The ink composition has a decaptime of greater than 15 seconds in a thermal ink jet printer.

The thermal ink jet ink composition of the invention has one or more ofthe following features: short dry times, long decap times, good adhesionto substrates, safety, and material compatibility. Decap time is definedas the amount of time a nozzle can remain dormant and then be firedagain without detrimental effect on the droplet velocity, weight ordirection. Fluids with good material compatibility are defined as thosewhich do not degrade the ability of the TIJ cartridge to fire for somecommercially reasonable length of time. The thermal ink jet inkcomposition does not require heat assist (e.g., thermal driers) whenprinted on semi-porous and non-porous substrates.

DETAILED DESCRIPTION OF THE INVENTION

The disclosure provides a thermal ink jet ink composition includingvolatile organic solvents, humectants, binder resins, colorants, and anadditive.

In an embodiment, the invention provides a thermal ink jet inkcomposition including one or more volatile organic solvents, one or morehumectants, one or more binder resins, and one or more dyes. Thehumectants are preferably present in an amount not more than 40% byweight of the thermal ink jet ink composition. The volatile organicsolvents may be selected from C₁-C₄ alcohols, C₄-C₈ ethers, C₃-C₆ketones, C₃-C₆ esters, and mixtures thereof.

The thermal ink jet ink composition includes an additive to extend thedecap time in a thermal ink jet printer. The additive is present in anamount greater than 0.01% by weight of the thermal ink jet inkcomposition. The additive preferably does not phase separate from theink jet composition during application of the ink to a substrate inthermal ink jet printing. The additive may be selected fromplasticizers, ionic surfactants, nonionic surfactants, aliphatichydrocarbons, drying oils, and mixtures thereof.

In accordance with an embodiment, the volatile organic solvents may beselected from C₁-C₄ alcohols, C₄-C₈ ethers, C₃-C₆ ketones, C₃-C₆ esters,and mixtures thereof. Examples of C₁-C₄ alcohols include methanol,ethanol, 1-propanol, and 2-propanol. Examples of C₄-C₈ ethers includediethyl ether, dipropyl ether, dibutyl ether and tetrahydrofuran.Examples of C₃-C₆ ketones include acetone, methyl ethyl ketone andcyclohexanone. Examples of C₃-C₆ esters include methyl acetate, ethylacetate and n-butyl acetate. The organic solvents, particularlyalcohols, ketones, and esters, have an attractive feature that theypenetrate semi- and non-porous substrate surfaces more readily thanwater based inks, thus reducing dry time and improving adhesion. One ormore volatile organic solvents may be present. In particular embodimentsthe thermal ink jet ink composition includes, as the volatile organicsolvent(s), methyl ethyl ketone, a blend of methyl ethyl ketone andmethanol, or a blend of methyl ethyl ketone and ethanol as the primaryjetting solvent.

The one or more volatile organic solvents may be present in any suitableamount, for example, in an amount 50% or more, about 60% or more, about70% or more, about 80% or more, or about 90% or more by weight of thethermal ink jet ink composition. In an embodiment, the one or morevolatile organic solvents may be present in an amount from 50% to about99%, preferably from about 60% to about 97%, and more preferably fromabout 80% to about 95% by weight of the thermal ink jet ink composition.The thermal ink jet ink composition may optionally include water in asuitable amount, e.g., up to 49% by weight, up to about 25% by weight,or up to about 10% by weight, up to about 5% by weight, or up to about2% by weight of the thermal ink jet ink composition.

The thermal ink jet ink composition may include any suitable colorant orcolorants, which may be dye or pigment. In an embodiment of theinvention, one or more dyes are employed as the colorant, wherein theone or more dyes are selected from acid dyes, basic dyes, solvent dyes,reactive dyes, disperse dyes, mordant dyes and any combination thereof.Examples of solvent dyes include naphthol dyes, azo dyes, metal complexdyes, anthraquinone dyes, quinoimine dyes, indigoid dyes, benzoquinonedyes, carbonium dyes, naphthoquinone dyes, naphthalimide dyes,phthalocyanine dyes, and perylene dyes. One or more colorants may bepresent.

For example, the thermal ink jet ink composition can include one or moredyes selected from C.I. Solvent Yellow 19, C.I. Solvent Yellow 21, C.I.Solvent Yellow 61, C.I. Solvent Yellow 80, C.I. Solvent Orange 1, C.I.Orange 37, C.I. Orange 40, C.I. Solvent Orange 54, C.I. Solvent Orange63, C.I. Solvent Red 8, Solvent Red 49, C.I. Solvent Red 81, C.I.Solvent Red 82, C.I. Solvent Red 84, C.I. Solvent Red 100, C.I. Acid Red92, C. I. Reactive red 31, Orient Pink 312, C.I. Basic Violet 3, C.I.Basic Violet 4, C.I. Solvent Violet 8, C.I. Solvent Violet 21, C.I.Solvent Blue 2, C.I. Solvent Blue 5, C.I. Solvent Blue 11, C.I. SolventBlue 25, C.I. Solvent Blue 36, C.I. Solvent Blue 38, C.I. Solvent Blue55; C.I. Solvent Blue 70, C.I. Solvent Green 3, C.I. Solvent Black 3,C.I. Solvent Black 5, C.I. Solvent Black 7, C.I. Solvent Black 22, C.I.Solvent Black 26, C.I. Solvent Black 27, C.I. Solvent Black 29 (VALIFASTBLACK 3808 or ORASOL RLI™), C.I. Acid Black 123, C.I. Solvent Black 48(MORFAST BLACK 101), C.I. Oil Blue 613, and any combination thereof, andpreferably one or more dyes selected from C.I. Solvent Black 29(VALIFAST BLACK™ 3808 or ORASOL BLACK Rum), C.I. Solvent Black 27, C.I.Solvent Black 48, C.I. Solvent Black 3 (Oil Black 860), C.I. BasicViolet 3, C.I. Solvent Blue 38, C.I. Solvent Blue 70, C.I. Oil Blue 613,C.I. Solvent Red 49 (ORIENT PINK™ 312), C.I. Solvent Orange 54 (VALIFASTORANGE™ 3210), and any combination thereof.

Any suitable pigment can be used, for example, one or more pigmentsselected from phthalocyanine blue, carbon black, mars black,quinacridone magenta, ivory black, prussian blue, cobalt blue,ultramarine blue, manganese blue, cerulean blue, indathrone blue,chromium oxide, iron oxides, viridian, cobalt green, terre verte, nickelazo yellow, light green oxide, phthalocyanine green-chlorinated copperphthalocyanine, burnt sienna, perinone orange, irgazin orange,quinacridone magenta, cobalt violet, ultramarine violet, manganeseviolet, dioxazine violet, zinc white, titanium white, flake white,aluminum hydrate, blanc fixe, china clay, lithophone, arylide yellow G,arylide yellow 10G, barium chromate, chrome yellow, chrome lemon, zincyellow, cadmium yellow, aureolin, naples yellow, nickel titanate,arylide yellow GX, isoindolinone yellow, flavanthrone yellow, yellowochre, chromophthal yellow 8GN, toluidine red, quinacridone red,permanent crimson, rose madder, alizarin crimson, vermilion, cadmiumred, permanent red FRG, brominated anthranthrone, naphthol carbamide,perylene red, quinacridone red, chromophthal red BRN, chromophthalscarlet R, aluminum oxide, bismuth oxide, cadmium oxide, chromium oxide,cobalt oxide, copper oxide, iridium oxide, lead oxide, manganese oxide,nickel oxide, rutile, silicon oxide, silver oxide, tin oxide, titaniumoxide, vanadium oxide, zinc oxide, zirconium oxide, and any combinationthereof.

In embodiments, the pigments are selected from azo pigments,phthalocyanine pigments, quinacridone pigments, dioxazine pigments,isoindolinone pigments, metal oxide pigments, carbon black, and anycombination thereof.

The pigments may have any suitable particle size, for example, fromabout 0.005 micron to about 15 microns, preferably from about 0.005 toabout 1 micron, and more preferably from about 0.01 to about 0.3 micron.

In any of the embodiments above, the colorant, dye or pigment, may bepresent in an amount from about 0.01% to about 10%, preferably fromabout 0.5% to about 7%, and more preferably from about 1% to about 5% byweight of the thermal ink jet ink composition.

In any of the embodiments above, any suitable humectant can be used.Preferably, humectants have a boiling point greater than 150 ° C.,greater than 200 ° C., or greater than 250° C., and/or a relativeevaporation rate less than 1.0, less than 0.9, less than 0.7, less than0.4, less than 0.1, or less than 0.01. The humectants typically aresolvents having one or more polar functional groups such as hydroxyl,ether, amide, ester, ketone, and carbonate, for example, two functionalgroups, which may be the same or different, such as two hydroxyl groupsor one hydroxyl group and one ether group. In an embodiment, the one ormore humectants are selected from polyol, glycol ether, diacetonealcohol, 2-pyrrolidinone, N-methylpyrrolidinone, ethyl lactate, butyllactate, propylene carbonate, 1,3-dimethyl-2-imidazolidindione, andalkyl esters, and any combination thereof.

For example, the polyol may be selected from polyethylene glycol,polypropylene glycol, poly(ethylene-co-propylene glycol), trimethylolpropane, ethylene glycol, glycerin, diethylene glycol, triethyleneglycol, tripropylene glycol, tetraethylene glycol, pentaethylene glycol,1,2-propylene glycol, 1,3-propanediol, butylene glycol, triethyleneglycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol,bis-2-hydroxyethyl ether, 1,4-butanediol, 1,2-butenediol,1,4-butenediol, 1,3-butenediol, 1,5-pentanediol, 2,4-pentanediol,2,4-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,1,2-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane,3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentylglycol, pentaerythritol, sorbitol, mannitol, and any combinationthereof, and preferably the polyol is selected from polyethylene glycol,trimethylol propane, ethylene glycol, propylene glycol, glycerin,diethylene glycol, tripropylene glycol, and any combination thereof,

A preferred humectant is glycol ether, for example, a glycol etherselected from ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, propylene glycol monomethyl ether, tripropylene glycolmonomethyl ether, ethylene glycol monobutyl ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, propylene glycoln-propyl ether, propylene glycol t-butyl ether, propylene glycol n-butylether, dipropylene glycol methyl ether, dipropylene glycol n-propylether, dipropylene glycol t-butyl ether, dipropylene glycol n-butylether, tripropylene glycol n-propyl ether, tripropylene glycol t-butylether, tripropylene glycol n-butyl ether, ethyl cellosolve, methylcellosolve, polyethylene glycol monomethyl ether, polypropylene glycolmonomethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol,1-butoxyethoxy-2-propanol, and any combination thereof, and preferably,the glycol ether is selected from ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, propylene glycol monomethyl ether(Propasol M), tripropylene glycol monomethyl ether, ethylene glycolmonobutyl ether, diethylene glycol monomethyl ether, diethylene glycolmonoethyl ether, propylene glycol monopropyl ether (Propasol P), and anycombination thereof. In certain embodiments, propylene glycol monomethylether is a preferred humectant. In other embodiments, propylene glycolmonopropyl ether is a preferred humectant.

Humectants may contribute, at least in part, to a feature of the thermalink jet ink composition. Thus, humectants may help lengthen decap times.In any of the embodiments, the one or more humectants may be present inany suitable amount, for example, in an amount about 40% or less,preferably about 30% or less, about 25% or less, about 20% or less,about 15% or less, or about 10% or less, by weight of the inkcomposition. The one or more humectants may be present in an amountabout 0.1%, 0.5%, 1%, 2%, or 5% or more by weight of the inkcomposition. In an embodiment, the one or more humectants may be presentin an amount from about 0.1% to about 30%, preferably from about 0.5% toabout 15%, and more preferably from about 1% to about 10% by weight ofthe thermal ink jet ink composition.

As discussed, the thermal ink jet ink composition includes one or morebinder resins. Any suitable binder resin, soluble or dispersible, can beemployed, preferably a solvent soluble binder resin. In an embodiment,the thermal ink jet ink composition includes one or more binder resinsselected from polyamide resins, polyurethane resins, rosin ester resins,acrylic resins, polyvinyl butyral resins, polyesters, phenolic resins,vinyl resins, polystyrene/polyacrylate copolymers, cellulose ethers,cellulose nitrate resins, polymaleic anhydrides, acetal polymers,polystyrene/polybutadiene copolymers, polystyrene/polymethacrylatecopolymers, sulfonated polyesters, aldehyde resins, polyhydroxystyreneresins, sulfonamide-modified epoxy resins, sulfonamide-modifiedformaldehyde resins, sulfonamide-modified melamine formaldehyde resinsand polyketone resins, and any combination thereof, and preferably oneor more binder resins selected from cellulose nitrate resins, polyamideresins, rosin ester resins, acrylic resins, polyvinyl butyral resins,vinyl resins, polyhydroxystyrene resins, sulfonamide-modified epoxyresins and any combination thereof. An example of a suitable polyamideresin is ARIZONA 201-150™ available from Arizona Chemical Company,Jacksonville, Fla., or COGNIS VERSAMID 756™, available from Cognis GmbH,Monheim am Rhein, Germany, both of which are alcohol-soluble polyamideresins. Examples of wood rosin ester resins include UNIREZ™ 8115,available as a 40% solution in ethanol from Penn Color, Doylestown, Pa.,which is a hydrogenated wood rosin ester, STAYBELITE™ ESTER 10,available from Chem Central Corporation and SUPERESTER™ A-75, availablefrom Arakawa-USA. Examples of cellulose nitrate resins are NOBEL™ DHX3-4, NOBEL™ DLX 3-5 or NOBEL™ DHX 5-8, available from Nobel Enterprises.Examples of polyvinyl butyral resins are PIOLOFORM™ BN18, available fromWacker Chemie AG, and MOWITAL™ B20H available from Kuraray America, Inc.Examples of acrylic and styrene/acrylic resins are JONCRYL™ 611, 682,and 586 (available from BASF, USA) and PARALOID™ B-66 and B-72(available from Dow Chemical, USA). Examples of vinyl resins includeUCAR™ VYHH, VMCH, YMCA, and VAGF (available from Dow Chemical Company,USA) and VINNOL™ E15/45, H14/36, E15/45M, and E16/40A (available fromWacker Chemie AG, Germany). Examples of polyhydroxystyrene resinsinclude P-HYDROXYSTYRENE BRANCHED GRADE PBS, available from HydriteChemical Company. Examples of sulfonamide-modified epoxy resins includeADPRO™ MTS (available from Rit-Chem).

The polymeric binder resin can be present in any suitable amount, forexample, in an amount from about 0.1% to about 30%, preferably fromabout 0.2% to about 15%, and more preferably from about 0.3% to about 8%of the thermal ink jet ink composition. The binder resin may be presentin an amount less than 15%, 12%, 10%, 8%, or 5% by weight of the inkcomposition.

In a particular embodiment of the thermal ink jet ink composition, thevolatile organic solvent or solvents may be present in an amount fromabout 50% to about 95% by weight, the colorant(s) (dyes, pigments, or acombination thereof), may be present in amount from about 1% to about 8%by weight, the humectant or humectants may be present in an amount fromabout 1% to 30% by weight, the binder resin or binder resins may bepresent in an amount from about 1% to about 8% by weight, and theadditive may be present in an amount from about 0.01% to 10% by weightof the thermal ink jet ink composition.

The thermal ink jet ink composition may further include one or moreadditives to extend decap time, such as plasticizers, ionic surfactants,nonionic surfactants, aliphatic hydrocarbons, drying oils, and mixturesthereof. The additive preferably does not phase separate from the inkjet composition during application of the ink to a substrate in thermalink jet printing. Examples of ionic and nonionic surfactants includesiloxanes, silicones, silanols, polyether modifiedpolydimethylsiloxanes, polyether modified polysiloxanes, ethoxylatedalcohols, propoxylated alcohols, alcohol ethoxylates, secondary alcoholethoxylates, polyoxyalkylenes, unmodified sulfosuccinates, monoestersulfosuccinates, diester sulfosuccinates, modified sulfosuccinates,amine alkylbenzene sulfonates, phosphate esters of an akylphenoxypolyethoxyethanol, polyoxoalkylenes, polyethylene glycol octylphenylethers, alkylated tallow amines, polyoxyalkyleneamines, propoxylated(poly(oxypropylene)) diamines, alkyl ether amines, nonyl phenolethoxylates, ethoxylated fatty amines, quaternized copolymers ofvinylpyrrolidone and dimethyl aminoethyl methacrylate, fluorinatedorganic acid diethanolamine salts, perfluoropolyethers, modifiedperfluoropolyethers, glycol-based perfluoroalkyl ethers, perfluoroalkylsubstituted polyethers, fluorinated polyacrylates, alkoxylatedethylenediamines, polyethylene oxides, polyoxyalkylene polyalkylenepolyamines, polyoxyalkylene polyalkylene polyimines, alkyl phosphateethoxylate mixtures, phosphate esters, polyglycol esters, diestersulfosuccinates, polyoxyalkylene derivatives of propylene glycol,organic esters, EO/PO block copolymers, acetylenic diols, ethoxylatedacetylenic diols, propoxylated acetylenic diols, acrylic blockcopolymers, hydrogenated castor oil and polyoxyethylated fatty alcohols.A specific example of a suitable polymeric surfactant, e.g., SiliconeFluid SF-69, available from Dow Corning Co, Midland, Mich., which is ablend of silanols and cyclic silicones. Additional examples of polymericsurfactants include DISPERSYBYK™ (BYK-Chemie, USA), SOLSPERSE™ (e.g.,SOLSPERSE 13940 which is a polymer/fatty acid condensation polymer) andEFKA™ (EFKA Chemicals) polymeric dispersants. Additional examples ofnon-ionic surfactants include ETHYLAN NS-500LQ (Akzo Nobel), SURFYNOL104 (Air Products), SERDOX™ ZTG-110 (Elementis), TERGITOL 15-S-7 (Dow),and MAKON™ DA-6 (Stepan). Additional examples of ionic surfactantsinclude ETHOPROPMEEN™ (AkzoNobel), G-3300 (Stepan), AEROSOL™ LF-4,AEROSOL™ WA-300 and AEROSOL™ OT-70 PG (Air Products).

In any of the embodiments, the surfactant additive may be present in anamount from about 0.01 to about 5.0% by weight, preferably from about0.05 to about 3% by weight of the thermal ink jet ink composition. Whena fluorinated surfactant is used, such as the above-listed fluorinatedorganic acid diethanolamine salts, perfluoropolyethers, modifiedperfluoropolyethers, glycol-based perfluoroalkyl ethers, perfluoroalkylsubstituted polyethers, fluorinated polyacrylates, it has been found,surprisingly and unexpectedly, that even a small amount of fluorinatedsurfactant can improve the decap time of the ink composition. Thus, thefluorinated surfactant may be present in an amount less than 0.1% byweight of the ink composition. In another embodiment, the fluorinatedsurfactant may be present in an amount less than 0.05% or less than0.03% by weight of the ink composition.

Examples of suitable plasticizers include phthalate plasticizers, e.g.,alkyl benzyl phthalates, butyl benzyl phthalate, dioctyl phthalate,diisobutyl phthalate, dicyclohexyl phthalate, diethyl phthalate,dimethyl isophthalate, dibutyl phthalate, and dimethyl phthalate, esterssuch as di-(2-ethylhexy)-adipate, diisobutyl adipate, glyceroltribenzoate, sucrose benzoate, polypropylene glycol dibenzoate,neopentyl glycol dibenzoate, dibutyl sebacate, andtri-n-hexyltrimellitate, and sulfonamide plasticizers such asPLASTICIZER 8, available from Monsanto Co., St. Louis, Mo., which isn-ethyl o,p-toluene sulfonamide.

In embodiments of the invention, the plasticizer additive may be presentin an amount from about 0.2 to about 5.0% by weight, preferably fromabout 0.3 to about 3.0%, and more preferably from about 0.5 to about2.0% of the thermal ink jet ink composition.

Examples of aliphatic hydrocarbons that may be used as additives includecyclic or straight chain hydrocarbons, either saturated or unsaturated.The aliphatic hydrocarbon additive may be present in an amount fromabout 0.1 to about 5.0% by weight, preferably from about 0.5 to about 2%by weight of the thermal ink jet ink composition.

Examples of drying oils that may be used as additives include tung oil,linseed oil, walnut oil, poppy seed oil and perilla oil. The drying oiladditive may be present in an amount from about 0.1 to about 5.0% byweight, preferably from about 0.5 to about 2% by weight of the thermalink jet ink composition.

The thermal ink jet ink composition may include additional ingredientssuch as bactericides, fungicides, algicides, sequestering agents,buffering agents, corrosion inhibitors, antioxidants, light stabilizers,anti-curl agents, thickeners, and other agents known in the relevantart. In an embodiment, the ink composition is free or substantially freeof antioxidants. The ink composition preferably includes no more thansmall amounts of water. In particular, the ink composition may includeless than 10%, 5%, 2%, 1%, 0.5%, or 0.1% by weight water. The inkcomposition may be substantially free of water.

The thermal ink jet ink composition has one or more attractive featuressuch as short unassisted dry times of printed alphanumeric or graphicimages, long decap times, good adhesion to semi-porous and non-poroussubstrates, and safety or material compatibility with one or morecomponents of a thermal ink jet printer. For example, embodiments of thethermal ink jet ink composition have a dry time of about 10 seconds orless, such as 5 seconds or less, 4 seconds or less, or 2 seconds orless, under ambient conditions. On porous substrates, the dry times areshorter than in semi- or non-porous substrates. For example, embodimentsof the thermal ink jet ink composition have a dry time of about 1 secondon porous substrates and less than about 5 seconds, preferably less thanabout 2 seconds, and more preferably less than about 1 second onsemi-porous substrates. The thermal ink jet ink composition preferablyhas a decap time of at least 15 seconds, more preferably at least 30seconds, more preferably at least 1 minute, 2 minutes, or 5 minutes, andmost preferably at least 10 minutes, when used in a thermal ink jetprint head.

The thermal ink jet ink composition may have any suitable viscosity orsurface tension. In embodiments of the invention, the thermal ink jetink composition has a viscosity of less than about 10 cPs, preferablyless than about 5 cPs, and more preferably less than about 3 cPs, forexample, a viscosity from about 1 to 4 or from about 1 to about 3 cPs at25° C.

In embodiments of the invention, the thermal ink jet ink composition hasa surface tension from about 18 to about 50 mN/m, from about 20 to about40 mN/m, or from about 22 to about 30 mN/m at 25° C.

The thermal ink jet ink composition may be prepared by any suitablemethod. For example, the chosen ingredients may be combined and mixedwith adequate stiffing and the resulting fluid filtered to remove anyundissolved impurities.

The present disclosure further provides a method for printing images ona substrate in a thermal ink jet printer comprising directing a streamof droplets of any of the embodiments of the thermal ink jet inkcomposition to a substrate and allowing the ink droplets to dry, therebyprinting images on a substrate. Any suitable substrate may be printed inaccordance with the invention. Examples of suitable substrates includeporous substrates such as uncoated paper, semi-porous substrates such asaqueous coated paper, clay coated paper, silica coated paper, UVovercoated paper, polymer overcoated paper, and varnish overcoatedpaper, and non-porous substrates such as hard plastics, polymer films,polymer laminates, metals, metal foil laminates, glass, and ceramics.The paper substrates may be thin sheets of paper, rolls of paper, orcardboard. Plastics, laminates, metals, glass, and ceramic substratesmay be in any suitable form such as in the form of bottles orcontainers, plates, rods, cylinders, etc.

Examples of polymer coating include a coating of polystyrene, polyvinylalcohol, polyacryate, polymethacrylate, polystryrene or polyvinylchloride. Examples of polymer film substrates include polyvinylbutyrals, polyolefins, polyvinyl chloride, polyethylene terephthalate,PETG, polybutylene terephthalate (PBT), polyester, polycarbonate,acrylonitrile-butadiene-styrene (ABS) copolymer, polyvinyl fluoridepolymer, polyamides, polyimides, and cellulose. Plastics may be treatedplastics (e.g. chemical etch, corona discharge, flame plasma, etc.) oruntreated plastics. Examples of metals include aluminum, copper,stainless steel, and metal alloys. Examples of ceramics include oxides,nitrides, and carbides of metals.

The following Examples further illustrate the invention but, of course,should not be construed as in any way limiting its scope. The followingExamples illustrate the preparation of an ink composition suitable foruse in a thermal ink printer. In each case, the ingredients werecombined and mixed until all solid components were dissolved. Theresulting mixture was filtered to remove any particulates and the inkcomposition was recovered. The ink composition was printed using arepresentative thermal ink jet printer on a variety of non-poroussubstrates including glass, aluminum, polyethylene, polypropylene,foils, polyester, polyamide and polyvinyl chloride. The decap time wasmeasured by one of two methods. Method 1 is by printing an imageconsisting of 100 vertical bars that were 1 dot wide for the full widthof the nozzle array, allowing the print head to remain idle for thespecified period of time, then reprinting the same image without wipingor other maintenance. The decap time is the maximum amount of time theprint head can remain uncapped and fully recover within the first 20% ofthe vertical lines. Method 2 of measuring the decap time is by printinga standard alphanumeric image repeatedly (between 10 and100 times),allowing the print head to remain idle for a specified period of time,then reprinting the same image without wiping or other maintenance.Method 1 was used for determining the decap time in Examples 1-4 below,and Method 2 was used for determining the decap time in Examples 5-10below. The decap time is the maximum amount of time the print head canremain uncapped and recover with a fully legible image. The drying timewas measured by printing representative alphanumeric text, and gentlysliding a finger across the text every second (or interval of seconds)and observing when the image no longer smears.

EXAMPLE 1

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 1 below. For the 5542 and 5543 samples,N-Ethyl O/P-Toluene Sulfonamide was used as an additive to increasedecap time. Comparative Example A did not include N-Ethyl O/P-TolueneSulfonamide.

TABLE 1 Comparative Example A 5542 5543 ethanol 67.45 66.45 65.45 glycolether PM 15 15 15 water 5 5 5 Arizona 201-150 (20% in ethanol) 10 10 10Silicone SF69 0.05 0.05 0.05 Solvent Red 49 1.5 1.5 1.5 Solvent Orange54 1.0 1.0 1.0 N-Ethyl O/P-Toluene Sulfonamide 1 2 Decap Time (seconds)8″ 15″  30″  Dry Time (seconds)—Semi-Porous 1″ 1″ 1″ Surface (Claycoated paper) Dry Time (seconds) Aqueous ≦5″    ≦5″    ≦5″    coatedpaper)

The printed images were found to have a drying time of 1 second or lesson semi-porous and 5 seconds or less on aqueous coated surfaces. Theimages had excellent rub resistance and adhesion properties. Sample 5543had a decap time of at least 30 seconds, compared to 8 seconds forComparative Example A.

EXAMPLE 2

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 2 below. For the 5572 and 5573 samples, asilicone surfactant was used as an additive to increase decap time.Comparative Example B did not include the silicone surfactant.

TABLE 2 Comparative Example B 5572 5573 ethanol 90.25 90.05 89.75 glycolether PM 3.13 3.13 3.13 Arizona 201-150 (20% in ethanol) 3.73 3.73 3.73Plasticizer 8 0.50 0.50 0.50 Solvent Red 49 1.39 1.39 1.39 SolventOrange 54 1.00 1.00 1.00 Silicone SF69 0.20 0.50 Decap Time (seconds)  8″ 30-60″ 120″ Dry Time (seconds)—Semi-Porous   1″   1″  1″ Surface(Clay coated paper) Dry Time (seconds)—Non-Porous 2.5″ 2.5″ 2.5″ Surface(Aqueous and Varnish coated paper)

The printed images were found to have a drying time of 1 second or lesson semi-porous surfaces and a drying time of 2.5 seconds on non-poroussurfaces. The images had excellent rub resistance and adhesionproperties. The images had acceptable print quality. Sample 5573 had adecap time of at least 2 minutes, compared to 8 seconds for ComparativeExample B.

EXAMPLE 3

The materials employed in preparing the thermal ink jet ink composition,their amounts, and the formulation numbers are set forth in Table 3below. For the 5605 sample, Magiesol 500/600 was used as an additive toincrease decap time. Comparative Example C did not include Magiesol500/600.

TABLE 3 Comparative Example C 5605 methanol 47.50 43.18 methyl ethylketone 47.50 43.18 Joncryl 682 3.47 3.16 Silicone SF69 0.03 0.03 BasicViolet 3 1.50 1.36 Magiesol 500/600 9.09 Decap Time (seconds) 15″ 300-600″ Dry Time (seconds)—Semi-Porous 1″ 1″ Surface (Clay coatedpaper) Dry Time (seconds)—Non-Porous 1″ >5″    Surface (Aqueous andVarnish coated paper)

The printed images were found to have a drying time of 1 second or lesson semi-porous surfaces. The images had excellent rub resistance andadhesion properties. The images had acceptable print quality. Sample5605 had a decap time of 5 to 10 minutes, compared to 15 seconds forComparative Example C.

EXAMPLE 4

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 4 below. For the 5600 sample, tung oilwas used as an additive to increase decap time. Comparative Example Ddid not include tung oil.

TABLE 4 Comparative Example D 5600 MEK 46.2 43.7 MeOH 46.2 43.7 glycolether PM 3.5 3.5 Joncryl 682 2 2 Silicone SF69 0.05 0.05 Basic Violet 32 2 Tung oil 5 Decap Time (seconds) 30-60″ >900″ Dry Time(seconds)—Semi-Porous 1″     1″ Surface (Clay coated paper) Dry Time(seconds)—Non-Porous 1″  >5″ Surface (Aqueous and Varnish coated paper)

The printed images were found to have a drying time of 1 second or lesson semi-porous surfaces. The images had excellent rub resistance andadhesion properties. Sample 5600 had a decap time of at least 15minutes, compared to 30-60 seconds for Comparative Example D.

EXAMPLE 5

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 5 below. Examples 6476 and 6481demonstrated that decap performance of the ink composition was improvedby the addition of SuperEster A-75, a wood rosin ester resin.

TABLE 5 Comparative Component Example E 6476 6481 ethanol SDA-3C 87.3386.4 85.35 Propasol P 5.56 5.56 6 Polyhydroxystyrene 2.78 2.78 3 resin(PHS) SuperEster A-75 0 0.93 1 Plasticizer 8 0.46 0.46 0.5 SF69 0.050.05 0.05 Silwet L 7622 0.09 0.09 0.1 Valifast Black 3808 3.01 3.25Valifast Black 3840 Orasol Black RLI 3.01 Valifast Orange 3210 0.69 0.690.75 total 100.0 100.0 100.0 DRY TIME <2 sec <2 sec <2 sec DECAP TIME 20sec >1 min >1 min

The printed images were found to have a drying time of 2 seconds or lesson non-porous surfaces. The images had excellent rub resistance andadhesion properties. Samples 6476 and 6481 had a decap times of at least1 minute, compared to 20 seconds for Comparative Example E.

EXAMPLE 6

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 6 below. The Fluorolink polymers used aremodified perfluoropolyethers. Fluorolink S10 is a fluorosurfactant thatis the reaction product of 3-(triethoxysilyl)-1-propanamine with ethylesters of reduced, polymerized oxidized poly (tetrafluroethylene).Fluorolink A10P is a fluorosurfactant that is the reaction product of1-octadecanamine with ethyl esters of reduced, polymerized oxidized poly(tetrafluroethylene). Fluorolink E10H is a fluorosurfactant that is anethoxylated diol derivative of reduced, polymerized oxidized poly(tetrafluroethylene). Capstone FS-3100 is a a fluorosurfactant that is apartially fluorinated alcohol substituted glycol.

Surprisingly and unexpectedly, Examples M-4, M-9, M-10 and M-11 alldemonstrated that addition of 0.25% or less of modified PFPE estersimproved decap times over Comparative Example F.

TABLE 6 Component Comparative Example F M-4 M-9 M-10 M-11 MEK 76.35 76.176.1 76.3 76.25 Propasol P 10 10 10 10 10 diacetone alcohol 6 6 6 6 6SuperEster A-75 3 3 3 3 3 Plasticizer 8 0.5 0.5 0.5 0.5 0.5 SF69 0.050.05 0.05 0.05 0.05 Silwet L 7622 0.1 0.1 0.1 0.1 0.1 Fluorolink S100.25 Fluorolink A10P 0.05 Fluorolink E10H 0.25 Capstone FS-3100 0.1Valifast Black 3808 3.25 3.25 3.25 3.25 3.25 Valifast Orange 3210 0.750.75 0.75 0.75 0.75 total 100.0 100.0 100.0 100.0 100.0 DRY TIME 3 sec 3sec 4 sec 4 sec 3 sec DECAP TIME 40 sec >1 min >1 min >1 min >1 min

The printed images were found to have a drying time of 4 seconds or lesson non-porous surfaces. The images had excellent rub resistance andadhesion properties. Samples M-4, M-9, M-10 and M-11 had decap times ofat least 1 minute, compared to 40 seconds for Comparative Example F.Comparative Example F did not contain a modified perfluoropolyether. Itwas unexpected that such a small amount of additive (less than 0.1% byweight of the ink composition) would dramatically improve the decapperformance of the ink composition.

EXAMPLE 7

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 7 below. Examples M-5, M-6 and M-8demonstrated that decap was improved by addition of 0.25% of FluorolinkS10.

TABLE 7 Comparative Ink # Example G M-6 M-8 MEK 77.85 77.60 77.67Propasol P 10.00 10.00 10.00 diacetone alcohol 6.00 6.00 6.00 SuperEsterA-75 1.50 1.50 1.50 Plasticizer 8 0.50 0.50 0.50 SF69 0.05 0.05 0.03Silwet L 7622 0.10 0.10 0.05 Fluorolink S10 0.25 0.25 Valifast Black3808 3.25 3.25 3.25 Valifast Orange 3210 0.75 0.75 0.75 total 100.0100.0 100.0 DRY TIME 5 sec 4 sec 4 sec DECAP TIME 40 sec >1 min >1 min

The printed images were found to have a drying time of 5 seconds or lesson non-porous surfaces. The images had excellent rub resistance andadhesion properties. Samples M-6 and M-8 had decap times of at greaterthan 1 minute, compared to 40 seconds for Comparative Example G.Comparative Example G did not contain a modified perfluoropolyether.

EXAMPLE 8

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 8 below.

TABLE 8 Comparative Component Example H PFPE-3 PFPE-8 PFPE-9 MEK 79.3679.16 79.16 79.31 Propasol P 10.88 10.85 10.85 10.88 diacetone alcohol1.86 1.86 1.86 1.86 Ad-Pro MTS 3.63 3.62 3.62 3.63 Plasticizer 8 0.490.49 0.49 0.49 SF69 0.05 0.05 0.05 0.05 Silwet L 7622 0.10 0.10 0.100.10 Fluorolink E10-H 0.25 Fluorolink A10-P 0.25 0.05 Valifast Black3808 2.94 2.93 2.93 2.94 Valifast Orange 3210 0.69 0.69 0.69 0.69 total100.0 100.0 100.0 100.0 DRY TIME 3 sec 3 sec 3 sec 30 sec DECAP TIME 30sec 50 sec >1 min >1 min

The printed images were found to have a drying time of 3 seconds or lesson non-porous surfaces. The images had excellent rub resistance andadhesion properties. Samples PFPE-3, PFPE-8, and PFPE-9 had decap timesof 50 seconds or longer, compared to 30 seconds for Comparative ExampleH. Comparative Example H did not contain a modified perfluoropolyether.

EXAMPLE 9

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 9 below. Trimethylolpropane and1,6-hexanediol are polyols. Chemphos TC-310 is an alkylphenolethoxylatephosphate ester. Stepfac 8170 and 8171 are phosphate esters of anakylphenoxy polyethoxyethanol. Stepfac 8180 and 8181 are phosphateesters of an akyl polyethoxyethanol. Dextrol OC-22 is the free acid formof a nonylphenol ethoxylated phosphate ester. Dextrol OC-70 is the freeacid form of a tridecyl alcohol ethoxylated phosphate ester.

TABLE 9 Comparative Component Example I M-12 M-13 M-14 M-15 M-16 1234812353 12349 M-17 M-18 12363 MEK 75.35 70.35 70.35 74.85 74.35 74.3572.35 72.35 72.35 72.35 72.35 72.35 Propasol P 10.00 10.00 10.00 10.0010.00 10.00 10 10 10 10 10 10 DiAce-OH 6.00 6.00 6.00 6.00 6.00 6.00 6 66 6 6 6 PHS 2.00 2.00 2.00 2.00 2.00 2.00 2 2 2 2 2 2 SE A-75 2.00 2.002.00 2.00 2.00 2.00 2 2 2 2 2 2 Plast-8 0.50 0.50 0.50 0.50 0.50 0.500.5 0.5 0.5 0.5 0.5 0.5 SF69 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 Silwet L7622 0.10 0.10 0.10 0.10 0.10 0.10 0.1 0.10.1 0.1 0.1 0.1 OB RLI 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.253.25 3.25 VO 3210 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.750.75 trimethylolpropane 5.00 1,6-hexanediol 5.00 Chemphos TC-310 0.501.00 sodium methane 1.00 sulfonate Stepfac 8170 3.00 Stepfac 8171 3.00Stepfac 8180 3.00 Stepfac 8181 3.00 Dextrol OC-22 3.00 Dextrol OC-703.00 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00100.00 100.00 100.00 100.00 DRY TIME 5 sec   5 sec  4 sec 5 sec DECAPTIME 2 min >5 min 45 sec 1 min

The printed images were found to have a drying time of 5 seconds or lesson non-porous surfaces. The images had excellent rub resistance andadhesion properties. Sample 13353 had a decap time of at least 5minutes, compared to 2 minutes for Comparative Example I. ComparativeExample I did not contain any polyol, sulfonate or phosphate esteradditives.

EXAMPLE 10

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Tables 10a and 10b below. Stepan G-3300 is anamine alkylbenzene sulfonate. Stepan DA-6, Tergitol 15-S-7, and Tergitol15-S-3 are alcohol ethoxylates. Ecosurf SA-4 is a mixture of ethoxylatedand propoxylated C6-C12 alcohols. Ethylan NS-500LQ is a polyoxoalkylene.Efka-3236 is a modified polysiloxane. Byk-331 and Edaplan LA412 arepolyether-modified polysiloxanes. Serdox ZTG-110 is a polyglycol ester.Aerosol LF-4, WA-300 and OT-70PG are modified or unmodifiedsulfosuccinates. Efka-4340 is an acrylic block copolymer.

TABLE 10a Comparative Component Example J 104-2 104-3 104-5 104-6 104-7104-8 104-9 MEK 76.35 75.85 75.85 75.85 75.85 75.85 75.85 75.85 PropasolP 10 10 10 10 10 10 10 10 diacetone alcohol 6 6 6 6 6 6 6 6 SuperEsterA-75 3 3 3 3 3 3 3 3 Plasticizer 8 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SF690.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Silwet L 7622 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 Stepan G-3300 0.5 Makon DA-6 0.5 EFKA-3236 0.5 Tergitol15-S-7 0.5 BYK-331 0.5 Ethylan NS-500LQ 0.5 Serdox ZTG-110 0.5 ValifastBlack 3808 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 Valifast Orange 32100.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 total 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0 DRY TIME <2 sec <2 sec <2 sec <2 sec <2 sec <2sec <2 sec  <2 sec DECAP TIME 20 sec 30 sec 40 sec 40 sec 50 sec 50 sec50 sec >90 sec

TABLE 10b Comparative Component Example J 104-10 104-11 104-12 104-13104-14 104-15 104.17 MEK 76.35 75.85 75.85 75.85 75.85 75.85 75.85 75.85Propasol P 10 10 10 10 10 10 10 10 diacetone alcohol 6 6 6 6 6 6 6 6SuperEster A-75 3 3 3 3 3 3 3 3 Plasticizer 8 0.5 0.5 0.5 0.5 0.5 0.50.5 0.5 SF69 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Silwet L 7622 0.10.1 0.1 0.1 0.1 0.1 0.1 0.1 Tergitol 15-S-3 0.5 Ecosurf SA-4 0.5 AerosolLF-4 0.5 Aerosol WA-300 0.5 Aerosol OT-70 PG 0.5 EFKA 4340 0.5 EdaplanLA 412 0.5 Valifast Black 3808 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25Valifast Orange 3210 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 total 100.0100.0 100.0 100.0 100.0 100.0 100.0 100.0 DRY TIME <2 sec  <2 sec <2 sec<2 sec <2 sec <2 sec <2 sec <2 sec DECAP TIME 20 sec >90 sec 60 sec 60sec 50 sec 70 sec 60 sec 50 sec

The printed images were found to have a drying time of 2 seconds or lesson non-porous surfaces. The images had excellent rub resistance andadhesion properties. Comparative Example I did not contain any aminealkylbenzene sulfonates, alcohol ethoxylates, ethoxylated andpropoxylated C6-C12 alcohols, polyoxoalkylenes, modified polysiloxanes,polyether-modified polysiloxanes, polyglycol esters, modifiedsulfosuccinates, unmodified sulfosuccinates, or acrylic blockcopolymers. The additives in the Examples were found to provide decaptimes of at least 30 seconds, which was longer than Comparative ExampleI

EXAMPLE 11

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing thethermal ink jet ink composition, their amounts, and the formulationnumbers are set forth in Table 11 below.

TABLE 11 Component 104-15 104-16 104-17 104-18 104-19 104-20 104-21104-22 104-23 104-24 104-25 104-26 MEK 75.85 75.85 75.85 75.85 75.8575.85 75.85 75.85 75.85 75.85 75.85 75.85 Propasol P 10 10 10 10 10 1010 10 10 10 10 10 diacetone alcohol 6 6 6 6 6 6 6 6 6 6 6 6 SuperEsterA-75 3 3 3 3 3 3 3 3 3 3 3 3 Plasticizer 8 0.5 0.5 0.5 0.5 0.5 0.5 0.50.5 0.5 0.5 0.5 0.5 SF69 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 Silwet L 7622 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 Ethopropmeen T/28 0.5 Troysol S366 0.5 Carbowet GA221 0.5 Surfynol104E 0.5 Ecosurf SA-4 0.5 Tergitol T-3 0.5 Triton X-15 0.5 StepanMWA-391 0.5 Capstone 1475 0.5 Hydrapol RP 0.5 FluorN 489 0.5 ChemguardS-554-100 0.5 Valifast Black 3808 3.25 3.25 3.25 3.25 3.25 3.25 3.253.25 3.25 3.25 3.25 3.25 Valifast Orange 3210 0.75 0.75 0.75 0.75 0.750.75 0.75 0.75 0.75 0.75 0.75 0.75 Total 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0 100.0 100.0 100.0

From the Examples above, it can be seen the various additives may beused in the thermal ink jet ink compositions disclosed herein to extendthe decap times in a thermal ink jet printer.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein may be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

What is claimed is:
 1. A thermal ink jet ink composition comprising: avolatile organic solvent; a binder resin, wherein the binder resin ispresent in an amount from 0.3% to 8% by weight of the ink composition; adye; a humectant in an amount from 1% to 40% by weight of the inkcomposition, and an additive for extending the decap time of the inkcomposition, wherein the additive is present in an amount less than 0.1%by weight of the ink composition, wherein the additive is selected fromthe group consisting of perfluoropolyethers, modifiedperfluoropolyethers, glycol-based perfluoroalkyl ethers, perfluoroalkylsubstituted polyethers, and mixtures thereof, and wherein if water ispresent, it is present in amount less than 10% by weight of the inkcomposition; wherein the ink composition has a decap time of greaterthan 15 seconds in a thermal ink jet printer.
 2. The thermal ink jet inkcomposition of claim 1, wherein the ink composition has a decap time ofgreater than 1 minute in a thermal ink jet printer.
 3. The thermal inkjet ink composition of claim 1, wherein the ink composition has a drytime of less than 5 seconds on a nonporous substrate when printed in athermal ink jet printer.
 4. A thermal ink jet cartridge including thethermal ink jet ink composition of claim
 1. 5. The thermal ink jet inkcomposition of claim 1, wherein the one or more volatile organicsolvents are selected from the group consisting of methanol, ethanol,1-propanol, isopropanol, acetone, methyl ethyl ketone, methyl propylketone, methyl i-propyl ketone, 3-pentanone, cyclohexanone, methylacetate, ethyl acetate, and mixtures thereof.
 6. The thermal ink jet inkcomposition of claim 1, wherein the binder resin is selected from thegroup consisting of polyamide resins, rosin ester resins, acrylicresins, polyketone resins, cellulose nitrate resins, polyvinyl butyralresins, vinyl resins, polyhydroxystyrene resins, sulfonamide-modifiedepoxy resins, and mixtures thereof.
 7. The thermal ink jet inkcomposition of claim 1, wherein the humectant is selected from the groupconsisting of polyol, glycol ether, diacetone alcohol, 2-pyrrolidinone,N-methylpyrrolidone, ethyl lactate, 1,3-dimethyl-2-imidazolidindione,propylene carbonate, alkyl esters, and mixtures thereof.
 8. A thermalink jet ink composition comprising: a volatile organic solvent; a binderresin, wherein the binder resin is present in an amount from 0.3% to 8%by weight of the ink composition; a dye; a humectant in an amount from1% to 40% by weight of the ink composition, and an ionic surfactantadditive for extending the decap time of the ink composition, whereinthe additive is present in an amount greater than 0.1% by weight of theink composition, wherein the additive is selected from the groupconsisting of unmodified sulfosuccinates, monoester sulfosuccinates,diester sulfosuccinates, modified sulfosuccinates, amine alkylbenzenesulfonates, alkoylated tallow amines, and mixtures thereof, and whereinif water is present, it is present in amount less than 10% by weight ofthe ink composition; wherein the ink composition has a decap time ofgreater than 15 seconds in a thermal ink jet printer.
 9. The thermal inkjet ink composition of claim 8, wherein the ink composition has a decaptime of greater than 1 minute in a thermal ink jet printer.
 10. Thethermal ink jet ink composition of claim 8, wherein the ink compositionhas a dry time of less than 5 seconds on a nonporous substrate whenprinted in a thermal ink jet printer.
 11. A thermal ink jet cartridgeincluding the thermal ink jet ink composition of claim
 8. 12. Thethermal ink jet ink composition of claim 8, wherein the one or morevolatile organic solvents are selected from the group consisting ofmethanol, ethanol, 1-propanol, isopropanol, acetone, methyl ethylketone, methyl propyl ketone, methyl i-propyl ketone, 3-pentanone,cyclohexanone, methyl acetate, ethyl acetate, and mixtures thereof. 13.The thermal ink jet ink composition of claim 8, wherein the binder resinis selected from the group consisting of polyamide resins, rosin esterresins, acrylic resins, polyketone resins, cellulose nitrate resins,polyvinyl butyral resins, vinyl resins, polyhydroxystyrene resins,sulfonamide-modified epoxy resins, and mixtures thereof.
 14. The thermalink jet ink composition of claim 8, wherein the humectant is selectedfrom the group consisting of polyol, glycol ether, diacetone alcohol,2-pyrrolidinone, N-methylpyrrolidone, ethyl lactate,1,3-dimethyl-2-imidazolidindione, propylene carbonate, alkyl esters, andmixtures thereof.
 15. A thermal ink jet ink composition comprising: avolatile organic solvent; a binder resin, wherein the binder resin ispresent in an amount from 0.3% to 8% by weight of the ink composition; adye; a humectant in an amount from 1% to 40% by weight of the inkcomposition, and a nonionic surfactant additive for extending the decaptime of the ink composition, wherein the additive is present in anamount greater than 0.1% by weight of the ink composition, wherein theadditive is selected from the group consisting of nonylphenol ethoxylatephosphates, polyalylated butyl ethers, polyglycol esters, polyethermodified polysiloxanes, phosphate esters of an akylphenoxypolyethoxyethanol, polyglycol esters, alcohol ethoxylates,polyoxoalkylenes, acrylic block copolymers, and mixtures thereof, andwherein if water is present, it is present in amount less than 10% byweight of the ink composition; wherein the ink composition has a decaptime of greater than 15 seconds in a thermal ink jet printer.
 16. Thethermal ink jet ink composition of claim 15, wherein the ink compositionhas a decap time of greater than 1 minute in a thermal ink jet printer.17. The thermal ink jet ink composition of claim 15, wherein the inkcomposition has a dry time of less than 5 seconds on a nonporoussubstrate when printed in a thermal ink jet printer.
 18. A thermal inkjet cartridge including the thermal ink jet ink composition of claim 15.19. The thermal ink jet ink composition of claim 15, wherein the one ormore volatile organic solvents are selected from the group consisting ofmethanol, ethanol, 1-propanol, isopropanol, acetone, methyl ethylketone, methyl propyl ketone, methyl i-propyl ketone, 3-pentanone,cyclohexanone, methyl acetate, ethyl acetate, and mixtures thereof. 20.The thermal ink jet ink composition of claim 15, wherein the binderresin is selected from the group consisting of polyamide resins, rosinester resins, acrylic resins, polyketone resins, cellulose nitrateresins, polyvinyl butyral resins, vinyl resins, polyhydroxystyreneresins, sulfonamide-modified epoxy resins, and mixtures thereof.
 21. Thethermal ink jet ink composition of claim 15, wherein the humectant isselected from the group consisting of polyol, glycol ether, diacetonealcohol, 2-pyrrolidinone, N-methylpyrrolidone, ethyl lactate,1,3-dimethyl-2-imidazolidindione, propylene carbonate, alkyl esters, andmixtures thereof.